CN113150290A - 阴离子型光响应嵌段共聚物接枝纳米纤维素的制备方法 - Google Patents
阴离子型光响应嵌段共聚物接枝纳米纤维素的制备方法 Download PDFInfo
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Abstract
本发明公开了阴离子型光响应嵌段共聚物接枝纳米纤维素的制备方法,取适量引发剂、含羧基亲水性大分子RAFT试剂、含环氧基乙烯类单体和溶剂混合反应,得到含羧基及环氧基单元的二嵌段共聚物;取适量引发剂、含羧基及环氧基单元的二嵌段共聚物、疏水性含氟单体、乙烯基香豆素单体和溶剂混合反应,得到阴离子型紫外光响应嵌段共聚物;将阴离子型紫外光响应嵌段共聚物、纳米纤维素、催化剂和溶剂混合反应,得到阴离子型光响应嵌段共聚物接枝纳米纤维素。本发明阴离子型光响应嵌段共聚物接枝纳米纤维素的制备方法,解决了现有技术中存在的纳米纤维素易自团聚的问题。
Description
技术领域
本发明涉及生物质功能高分子材料技术领域,具体涉及阴离子型光响应嵌段共聚物接枝纳米纤维素的制备方法。
背景技术
纳米纤维素(CNC)是由纤维素通过化学、机械或酶解等不同方法制备的,是可再生和可生物降解的针状纳米粒子,通常长度为50-350nm,宽度为5-20nm。与其他尺寸的纤维素相比,CNC具有较高的强度、弹性模量、结晶度等特点。近年来,CNC已在食品、医药、功能材料等领域被广泛用作纳米材料设计的基石。但是,由于极强的亲水性,CNC在疏水性溶剂和聚合物介质中的分散性较差,因此对CNC进行适当的功能化改性,改善其亲水/疏水性、相容性和反应活性,拓展其应用领域,成为目前纳米纤维素研究的热点。
目前,普遍的改性方法包括非共价键及化学键改性方法。其中,化学键改性法较为常用。CNC的化学键改性方法一般概括为两类:(1)、小分子衍生化修饰(包括酯化、硅烷化、异氰酸酯化和阳离子化等);(2)聚合物接枝反应(包括“grafting to”和“grafting from”策略)。此外,还有通过在CNC表面引入刺激响应性基团或分子,用以开发具有光学、力学、电磁学等特殊性质的功能纳米材料的改性方法。在各种刺激中,光作为一种典型的外部刺激,具有光源安全、清洁,良好的可控性和可调节性等优点。但是上述方法中当疏水性烷基链或聚合物链接枝到CNC表面时,CNC被不可逆转地改变为增加疏水性。
发明内容
本发明的目的是提供阴离子型光响应嵌段共聚物接枝纳米纤维素的制备方法,解决了现有技术中存在的纳米纤维素易自团聚的问题。
本发明所采用的技术方案是阴离子型光响应嵌段共聚物接枝纳米纤维素的制备方法,具体按照以下步骤实施:
步骤1、取适量引发剂、含羧基亲水性大分子RAFT试剂、含环氧基乙烯类单体和溶剂混合反应,得到含羧基及环氧基单元的二嵌段共聚物;
步骤2、取适量引发剂、含羧基及环氧基单元的二嵌段共聚物、疏水性含氟单体、乙烯基香豆素单体和溶剂混合反应,得到阴离子型紫外光响应嵌段共聚物;
步骤3、将阴离子型紫外光响应嵌段共聚物、纳米纤维素、催化剂和溶剂混合反应,得到阴离子型光响应嵌段共聚物接枝纳米纤维素。
本发明的特点还在于:
引发剂为偶氮二异丁腈、偶氮二异庚腈或4,4'-偶氮双(4-氰基戊酸)。
步骤1具体为:
步骤1.1、按质量比为1~3:30~90:50~160:700~1500分别称取引发剂、含羧基亲水性大分子RAFT试剂、含环氧基乙烯类单体和溶剂,然后置于装有磁子的反应器中;
步骤1.2、将反应器置于油浴中,于室温下先通入20~30min的氩气,然后将反应器升温至40℃~65℃,使引发剂、含羧基亲水性大分子RAFT试剂和含环氧基乙烯类单体在氩气保护下反应5~12h,得到产物;
步骤1.3、将产物于正己烷中沉淀提纯后,得到含羧基及环氧基单元的二嵌段共聚物。
溶剂为1,4-二氧六环、苯或N,N-二甲基甲酰胺;含羧基亲水性大分子RAFT试剂为聚甲基丙烯酸大分子RAFT试剂或聚丙烯酸大分子RAFT试剂;含环氧基乙烯类单体为甲基丙烯酸缩水甘油酯或丙烯酸缩水甘油酯。
步骤2具体为:
步骤2.1、按质量比为1:30~130:8~85:4~50:700~2500分别称取引发剂、含羧基及环氧基单元的二嵌段共聚物、疏水性含氟单体、乙烯基香豆素单体和溶剂,然后置于装有磁子的反应器中,充分搅拌至溶解;
步骤2.2、将反应器置于油浴中,于室温下先通入20~30min的氩气,然后将反应器升温至60℃~80℃,使引发剂、含羧基及环氧基单元的二嵌段共聚物、疏水性含氟单体和乙烯基香豆素单体在氩气保护下反应7~10h,得到产物;
步骤2.3、将产物于正己烷中沉淀提纯后于真空烘箱干燥,得到阴离子型紫外光响应嵌段共聚物。
溶剂为1,4-二氧六环、四氢呋喃、苯或N,N-二甲基甲酰胺;疏水性含氟单体为甲基丙烯酸2,2,2-三氟乙酯、丙烯酸六氟丁酯或甲基丙烯酸六氟丁酯;乙烯基香豆素单体为7-(6-(丙烯酰氧基己氧基)-4-甲基香豆素、7-(2-甲基丙烯酰氧基)-4-甲基香豆素或7-(2-丙烯酸酯基乙氧基)-4-甲基香豆素。
步骤3具体为:
步骤3.1、按质量比为5:5~25:165:1~20分别称取纳米纤维素、阴离子型紫外光响应嵌段共聚物、溶剂和催化剂于反应容器中;
步骤3.2、将反应容器置于油浴中,升温至50℃~120℃,使纳米纤维素、阴离子型紫外光响应嵌段共聚物、溶剂和催化剂充分反应12h~36h,得到产物;
步骤3.3、采用离心机将产物离心处理后,通过四氢呋喃洗涤3~4次,置于真空烘箱中干燥后得到阴离子型光响应嵌段共聚物接枝纳米纤维素。
溶剂为N,N-二甲基甲酰胺或二甲基亚砜;催化剂为三乙胺、4-二甲氨基吡啶、吡啶或四丁基溴化铵。
含羧基亲水性大分子RAFT试剂的分子量为3000~8000。
本发明的有益效果是:
本发明阴离子型光响应嵌段共聚物接枝纳米纤维素的制备方法,该阴离子型光响应嵌段共聚物接枝纳米纤维素可应用于响应性Pickering稳定剂、光响应填料、光控膜、药物释放等,本发明的制备方法重复性好,技术路线可为其他环境响应性聚合物智能材料研究提供良好思路;
本发明阴离子型光响应嵌段共聚物接枝纳米纤维素的制备方法,通过RAFT聚合技术合成分子量可控的阴离子型紫外光响应嵌段共聚物,即通过阴离子型紫外光响应嵌段共聚物带有的活性环氧基团与纳米纤维素上的羟基反应,将其接枝到纳米纤维素表面以解决纳米纤维素易自团聚的问题,并通过调节亲水嵌段及疏水嵌段比例,使纳米纤维具备可调谐的表面润湿性;
本发明制备的阴离子型光响应嵌段共聚物接枝纳米纤维素具有紫外光响应特性。
附图说明
图1为本发明阴离子型光响应嵌段共聚物接枝纳米纤维素在365nm的紫外光照射下的紫外吸收谱图;
图2为本发明阴离子型光响应嵌段共聚物接枝纳米纤维素在254nm的紫外光照射下的紫外吸收谱图;
图3为纳米纤维素分别在水、DMF、THF、CHCl3、Toluene中的分散结果图;
图4为本发明阴离子型光响应嵌段共聚物接枝纳米纤维素分别在水、DMF、THF、CHCl3、Toluene中的分散结果图。
具体实施方式
下面结合附图和具体实施方式对本发明进行详细说明。
本发明提出了阴离子型光响应嵌段共聚物接枝纳米纤维素的制备方法,具体按照以下步骤实施:
步骤1、取适量引发剂、含羧基亲水性大分子RAFT试剂、含环氧基乙烯类单体和溶剂混合反应,得到含羧基及环氧基单元的二嵌段共聚物,具体为:
步骤1.1、按质量比为1~3:30~90:50~160:700~1500分别称取引发剂、含羧基亲水性大分子RAFT试剂、含环氧基乙烯类单体和溶剂,然后置于装有磁子的反应器中;
步骤1.2、将反应器置于油浴中,于室温下先通入20~30min的氩气,然后将反应器升温至40℃~65℃,使引发剂、含羧基亲水性大分子RAFT试剂和含环氧基乙烯类单体在氩气保护下反应5~12h,得到产物;
步骤1.3、将产物于正己烷中沉淀提纯后,得到含羧基及环氧基单元的二嵌段共聚物;
其中,引发剂为偶氮二异丁腈、偶氮二异庚腈或4,4'-偶氮双(4-氰基戊酸);溶剂为1,4-二氧六环、苯或N,N-二甲基甲酰胺;含羧基亲水性大分子RAFT试剂为聚甲基丙烯酸大分子RAFT试剂或聚丙烯酸大分子RAFT试剂;含环氧基乙烯类单体为甲基丙烯酸缩水甘油酯或丙烯酸缩水甘油酯;含羧基亲水性大分子RAFT试剂的分子量为3000~8000。
步骤2、取适量引发剂、含羧基及环氧基单元的二嵌段共聚物、疏水性含氟单体、乙烯基香豆素单体和溶剂混合反应,得到阴离子型紫外光响应嵌段共聚物;具体为:
步骤2.1、按质量比为1:30~130:8~85:4~50:700~2500分别称取引发剂、含羧基及环氧基单元的二嵌段共聚物、疏水性含氟单体、乙烯基香豆素单体和溶剂,然后置于装有磁子的反应器中,充分搅拌至溶解;
步骤2.2、将反应器置于油浴中,于室温下先通入20~30min的氩气,然后将反应器升温至60℃~80℃,使引发剂、含羧基及环氧基单元的二嵌段共聚物、疏水性含氟单体和乙烯基香豆素单体在氩气保护下反应7~10h,得到产物;
步骤2.3、将产物于正己烷中沉淀提纯后于真空烘箱干燥,得到阴离子型紫外光响应嵌段共聚物;
其中,溶剂为1,4-二氧六环、四氢呋喃、苯或N,N-二甲基甲酰胺;疏水性含氟单体为甲基丙烯酸2,2,2-三氟乙酯、丙烯酸六氟丁酯或甲基丙烯酸六氟丁酯;乙烯基香豆素单体为7-(6-(丙烯酰氧基己氧基)-4-甲基香豆素、7-(2-甲基丙烯酰氧基)-4-甲基香豆素或7-(2-丙烯酸酯基乙氧基)-4-甲基香豆素;引发剂为偶氮二异丁腈、偶氮二异庚腈或4,4'-偶氮双(4-氰基戊酸);
步骤3、将阴离子型紫外光响应嵌段共聚物、纳米纤维素、催化剂和溶剂混合反应,得到阴离子型光响应嵌段共聚物接枝纳米纤维素;具体为:
步骤3.1、按质量比为5:5~25:165:1~20分别称取纳米纤维素、阴离子型紫外光响应嵌段共聚物、溶剂和催化剂于反应容器中;
步骤3.2、将反应容器置于油浴中,升温至50℃~120℃,使纳米纤维素、阴离子型紫外光响应嵌段共聚物、溶剂和催化剂充分反应12h~36h,得到产物;
步骤3.3、采用离心机将产物离心处理后,通过四氢呋喃洗涤3~4次,置于真空烘箱中干燥后得到阴离子型光响应嵌段共聚物接枝纳米纤维素。
其中,溶剂为N,N-二甲基甲酰胺或二甲基亚砜;催化剂为三乙胺、4-二甲氨基吡啶、吡啶或四丁基溴化铵。
实施例1
阴离子型光响应嵌段共聚物接枝纳米纤维素的制备方法:
(1)制备含羧基及环氧基单元的二嵌段共聚物
按质量比为1:90:152:1417分别称取偶氮二异丁腈、含羧基亲水性大分子RAFT试剂、甲基丙烯酸缩水甘油酯和1,4-二氧六环,然后置于装有磁子的三口烧瓶中,搅拌溶解后形成混合液;
将三口烧瓶置于油浴中,于室温下先通入30min的氩气,然后将三口烧瓶升温至50℃,使偶氮二异丁腈、含羧基亲水性大分子RAFT试剂、甲基丙烯酸缩水甘油酯在氩气保护下反应8h,得到产物;
将产物于正己烷中沉淀提纯后,得到含羧基及环氧基单元的二嵌段共聚物;
(2)制备阴离子型紫外光响应嵌段共聚物
按质量比为1:50:8:10:760分别称取偶氮二异丁腈、含羧基及环氧基单元的二嵌段共聚物、丙烯酸六氟丁酯、7-(6-(丙烯酰氧基己氧基)-4-甲基香豆素和1,4-二氧六环,然后置于装有磁子的三口烧瓶中,充分搅拌至溶解;
将三口烧瓶置于油浴中,于室温下先通入30min的氩气,然后将三口烧瓶升温至80℃,使偶氮二异丁腈、含羧基及环氧基单元的二嵌段共聚物、丙烯酸六氟丁酯和7-(6-(丙烯酰氧基己氧基)-4-甲基香豆素在氩气保护下反应8h,得到产物;
将产物于正己烷中沉淀提纯后于真空烘箱干燥,得到阴离子型紫外光响应嵌段共聚物;
(3)制备阴离子型光响应嵌段共聚物接枝纳米纤维素
步骤3.1、按质量比为5:15:20:165分别称取纳米纤维素、阴离子型紫外光响应嵌段共聚物、三乙胺和N,N-二甲基甲酰胺于烧瓶中;
步骤3.2、将烧瓶置于油浴中,升温至120℃,使纳米纤维素、阴离子型紫外光响应嵌段共聚物、三乙胺和N,N-二甲基甲酰胺充分反应24h,得到产物;
步骤3.3、采用离心机将产物离心处理后,通过四氢呋喃洗涤3~4次,置于真空烘箱中干燥后得到阴离子型光响应嵌段共聚物接枝纳米纤维素。
实施例2
阴离子型光响应嵌段共聚物接枝纳米纤维素的制备方法:
(1)制备含羧基及环氧基单元的二嵌段共聚物
按质量比为1:45:50:713分别称取4,4'-偶氮双(4-氰基戊酸)、含羧基亲水性大分子RAFT试剂、甲基丙烯酸缩水甘油酯和1,4-二氧六环,然后置于装有磁子的三口烧瓶中,搅拌溶解后形成混合液;
将三口烧瓶置于油浴中,于室温下先通入30min的氩气,然后将三口烧瓶升温至60℃,使4,4'-偶氮双(4-氰基戊酸)、含羧基亲水性大分子RAFT试剂和甲基丙烯酸缩水甘油酯在氩气保护下反应6h,得到产物;
将产物于正己烷中沉淀提纯后,得到含羧基及环氧基单元的二嵌段共聚物;
(2)制备阴离子型紫外光响应嵌段共聚物
按质量比为1:50:67:20:1450分别称取偶氮二异丁腈、含羧基及环氧基单元的二嵌段共聚物、甲基丙烯酸六氟丁酯、7-(2-甲基丙烯酰氧基)-4-甲基香豆素和1,4-二氧六环,然后置于装有磁子的三口烧瓶中,充分搅拌至溶解;
将三口烧瓶置于油浴中,于室温下先通入30min的氩气,然后将三口烧瓶升温至80℃,使偶氮二异丁腈、含羧基及环氧基单元的二嵌段共聚物、甲基丙烯酸六氟丁酯、7-(2-甲基丙烯酰氧基)-4-甲基香豆素在氩气保护下反应8h,得到产物;
将产物于正己烷中沉淀提纯后于真空烘箱干燥,得到阴离子型紫外光响应嵌段共聚物;
(3)制备阴离子型光响应嵌段共聚物接枝纳米纤维素
步骤3.1、按质量比为5:10:1:165分别称取纳米纤维素、阴离子型紫外光响应嵌段共聚物、4-二甲氨基吡啶和N,N-二甲基甲酰胺于烧瓶中;
步骤3.2、将烧瓶置于油浴中,升温至50℃,使纳米纤维素、阴离子型紫外光响应嵌段共聚物、4-二甲氨基吡啶和N,N-二甲基甲酰胺充分反应36h,得到产物;
步骤3.3、采用离心机将产物离心处理后,通过四氢呋喃洗涤3~4次,置于真空烘箱中干燥后得到阴离子型光响应嵌段共聚物接枝纳米纤维素。
实施例3
阴离子型光响应嵌段共聚物接枝纳米纤维素的制备方法:
(1)制备含羧基及环氧基单元的二嵌段共聚物
按质量比为3:30:50:800分别称取4,4'-偶氮双(4-氰基戊酸)、含羧基亲水性大分子RAFT试剂、甲基丙烯酸缩水甘油酯和1,4-二氧六环,然后置于装有磁子的三口烧瓶中,搅拌溶解后形成混合液;
将三口烧瓶置于油浴中,于室温下先通入30min的氩气,然后将三口烧瓶升温至65℃,使4,4'-偶氮双(4-氰基戊酸)、含羧基亲水性大分子RAFT试剂、甲基丙烯酸缩水甘油酯在氩气保护下反应5h,得到产物;
将产物于正己烷中沉淀提纯后,得到含羧基及环氧基单元的二嵌段共聚物;
(2)制备阴离子型紫外光响应嵌段共聚物
按质量比为1:130:85:30:2447分别称取偶氮二异丁腈、含羧基及环氧基单元的二嵌段共聚物、甲基丙烯酸六氟丁酯、7-(2-甲基丙烯酰氧基)-4-甲基香豆素和1,4-二氧六环,然后置于装有磁子的三口烧瓶中,充分搅拌至溶解;
将三口烧瓶置于油浴中,于室温下先通入30min的氩气,然后将三口烧瓶升温至70℃,使偶氮二异丁腈、含羧基及环氧基单元的二嵌段共聚物、甲基丙烯酸六氟丁酯、7-(2-甲基丙烯酰氧基)-4-甲基香豆素在氩气保护下反应8h,得到产物;
将产物于正己烷中沉淀提纯后于真空烘箱干燥,得到阴离子型紫外光响应嵌段共聚物;
(3)制备阴离子型光响应嵌段共聚物接枝纳米纤维素
步骤3.1、按质量比为5:25:1:165分别称取纳米纤维素、阴离子型紫外光响应嵌段共聚物、三乙胺和二甲基亚砜于烧瓶中;
步骤3.2、将烧瓶置于油浴中,升温至120℃,使纳米纤维素、阴离子型紫外光响应嵌段共聚物、三乙胺和二甲基亚砜充分反应12h,得到产物;
步骤3.3、采用离心机将产物离心处理后,通过四氢呋喃洗涤3~4次,置于真空烘箱中干燥后得到阴离子型光响应嵌段共聚物接枝纳米纤维素。
实验验证:
1.光响应性测试
图1是MCNC水分散液的紫外吸收光谱图,可知MCNC水分散液在320nm处有紫外吸收峰,在365nm光照条件下,随着光照时间的延长,MCNC水分散液的紫外吸光度逐渐下降,这是因为在365nm光照条件下香豆素单体之间发生光二聚反应,使吡喃酮环上双键消失,减少了π-π*电子跃迁,导致在320nm处特征吸收峰强度随UV光照时间的增加而下降。将阴离子型光响应嵌段共聚物接枝纳米纤维素置于254nm紫外灯下照射,由图2可知,随着光照时间的延长,320nm处紫外吸收峰又逐渐增强,表明在该条件下,香豆素单体光致二聚化程度逐渐降低,发生解交联。
上述实验结果表明,光响应性两亲性三嵌段共聚物成功接枝到纳米纤维素表面,且经光响应性两亲性嵌段共聚物改性后的纳米纤维素具有光响应特性。
2.在水、DMF、THF、CHCl3、Toluene中分别对纳米纤维素、本发明阴离子型光响应嵌段共聚物接枝纳米纤维素进行分散测试
由图3可知,原始纳米纤维素不仅在水中具有良好的分散性,在DMF中也分散得比较好;但是,随着溶剂疏水性的增强,原始纳米纤维素的分散性降低,在极性较弱的甲苯溶剂中,极易团聚。而本发明的阴离子型光响应嵌段共聚物接枝纳米纤维素除了能在极性较强的水、DMF中分散外,还在极性较弱的甲苯溶剂具有良好的分散性,这说明经改性后的纳米纤维素在非极性溶剂中具有良好的分散性。
Claims (9)
1.阴离子型光响应嵌段共聚物接枝纳米纤维素的制备方法,其特征在于,具体按照以下步骤实施:
步骤1、取适量引发剂、含羧基亲水性大分子RAFT试剂、含环氧基乙烯类单体和溶剂混合反应,得到含羧基及环氧基单元的二嵌段共聚物;
步骤2、取适量引发剂、含羧基及环氧基单元的二嵌段共聚物、疏水性含氟单体、乙烯基香豆素单体和溶剂混合反应,得到阴离子型紫外光响应嵌段共聚物;
步骤3、将所述阴离子型紫外光响应嵌段共聚物、纳米纤维素、催化剂和溶剂混合反应,得到阴离子型光响应嵌段共聚物接枝纳米纤维素。
2.根据权利要求1所述的阴离子型光响应嵌段共聚物接枝纳米纤维素的制备方法,其特征在于,所述引发剂为偶氮二异丁腈、偶氮二异庚腈或4,4'-偶氮双(4-氰基戊酸)。
3.根据权利要求1所述的阴离子型光响应嵌段共聚物接枝纳米纤维素的制备方法,其特征在于,步骤1具体为:
步骤1.1、按质量比为1~3:30~90:50~160:700~1500分别称取引发剂、含羧基亲水性大分子RAFT试剂、含环氧基乙烯类单体和溶剂,然后置于装有磁子的反应器中;
步骤1.2、将所述反应器置于油浴中,于室温下先通入20~30min的氩气,然后将所述反应器升温至40℃~65℃,使引发剂、含羧基亲水性大分子RAFT试剂和含环氧基乙烯类单体在氩气保护下反应5~12h,得到产物;
步骤1.3、将所述产物于正己烷中沉淀提纯后,得到所述含羧基及环氧基单元的二嵌段共聚物。
4.根据权利要求3所述的阴离子型光响应嵌段共聚物接枝纳米纤维素的制备方法,其特征在于,所述溶剂为1,4-二氧六环、苯或N,N-二甲基甲酰胺;所述含羧基亲水性大分子RAFT试剂为聚甲基丙烯酸大分子RAFT试剂或聚丙烯酸大分子RAFT试剂;所述含环氧基乙烯类单体为甲基丙烯酸缩水甘油酯或丙烯酸缩水甘油酯。
5.根据权利要求3所述的阴离子型光响应嵌段共聚物接枝纳米纤维素的制备方法,其特征在于,步骤2具体为:
步骤2.1、按质量比为1:30~130:8~85:4~50:700~2500分别称取引发剂、含羧基及环氧基单元的二嵌段共聚物、疏水性含氟单体、乙烯基香豆素单体和溶剂,然后置于装有磁子的反应器中,充分搅拌至溶解;
步骤2.2、将所述反应器置于油浴中,于室温下先通入20~30min的氩气,然后将所述反应器升温至60℃~80℃,使引发剂、含羧基及环氧基单元的二嵌段共聚物、疏水性含氟单体和乙烯基香豆素单体在氩气保护下反应7~10h,得到产物;
步骤2.3、将所述产物于正己烷中沉淀提纯后于真空烘箱干燥,得到所述阴离子型紫外光响应嵌段共聚物。
6.根据权利要求5所述的阴离子型光响应嵌段共聚物接枝纳米纤维素的制备方法,其特征在于,所述溶剂为1,4-二氧六环、四氢呋喃、苯或N,N-二甲基甲酰胺;所述疏水性含氟单体为甲基丙烯酸2,2,2-三氟乙酯、丙烯酸六氟丁酯或甲基丙烯酸六氟丁酯;所述乙烯基香豆素单体为7-(6-(丙烯酰氧基己氧基)-4-甲基香豆素、7-(2-甲基丙烯酰氧基)-4-甲基香豆素或7-(2-丙烯酸酯基乙氧基)-4-甲基香豆素。
7.根据权利要求5所述的阴离子型光响应嵌段共聚物接枝纳米纤维素的制备方法,其特征在于,步骤3具体为:
步骤3.1、按质量比为5:5~25:165:1~20分别称取纳米纤维素、阴离子型紫外光响应嵌段共聚物、溶剂和催化剂于反应容器中;
步骤3.2、将所述反应容器置于油浴中,升温至50℃~120℃,使纳米纤维素、阴离子型紫外光响应嵌段共聚物、溶剂和催化剂充分反应12h~36h,得到产物;
步骤3.3、采用离心机将所述产物离心处理后,通过四氢呋喃洗涤3~4次,置于真空烘箱中干燥后得到所述阴离子型光响应嵌段共聚物接枝纳米纤维素。
8.根据权利要求7所述的阴离子型光响应嵌段共聚物接枝纳米纤维素的制备方法,其特征在于,所述溶剂为N,N-二甲基甲酰胺或二甲基亚砜;所述催化剂为三乙胺、4-二甲氨基吡啶、吡啶或四丁基溴化铵。
9.根据权利要求1所述的阴离子型光响应嵌段共聚物接枝纳米纤维素的制备方法,其特征在于,所述含羧基亲水性大分子RAFT试剂的分子量为3000~8000。
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